Production system of glyphosate technical
By optimizing the glyphosate production process, using phosphorus trichloride, dimethyl phosphite and glyphosate processes, combined with the esterification reaction and the use of catalysts, the problems of wastewater pollution and low production efficiency in the prior art have been solved, and efficient and low-pollution glyphosate production has been achieved.
Patent Information
- Application Number
- CN202411842046.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-13
- Publication Date
- 2025-03-28
AI Technical Summary
In the existing glyphosate production process, the glycine method makes wastewater pollution difficult to deal with and low production efficiency; the IDA method relies on imports to increase cost uncertainty, and the equipment and operating conditions are harsh.
The phosphorus trichloride process, dimethyl phosphite process and glyphosate process are adopted to optimize the production process of glyphosate through the esterification reaction, deacidification process and the use of catalysts, and improve production efficiency and product purity.
It reduces wastewater pollution, reduces production costs, improves the purity and yield of glyphosate, and the crosslinking structure of the catalyst improves catalytic efficiency and mechanical strength.
Smart Images
Figure CN119708051A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of pesticide production, and in particular to a production system of glyphosate technical. Background Art
[0002] Glyphosate, with the chemical name N-(phosphonomethyl)glycine and the molecular formula C3H8NO5P, is a highly effective broad-spectrum herbicide that has a control effect on more than 40 families of plants, including monocots and dicots, annuals and perennials, herbs and shrubs. Glyphosate is known for its strong systemic conductivity and has a strong destructive power on the underground tissues of perennial deep-rooted weeds, reaching depths that general agricultural machinery cannot reach. The main principle of glyphosate's weed control is to inhibit the conversion of shikizone to phenylalanine, tyrosine and tryptophan, interfere with the synthesis of plant proteins, and thus cause plant death. Glyphosate has a wide range of application scenarios. On the one hand, it is used for weeding of conventional crops, such as inter-row weeding in orchards, tea mulberry, rubber plantations, and sugarcane plantations, and weeding of no-till crops such as rice fields and wheat fields. It is also used for weeding in forests and fire isolation belts, railways, airports, and highways, and for grassland improvement. On the other hand, with the development of genetic modification technology, glyphosate has also been widely used in weed control of glyphosate-resistant genetically modified crops, such as soybeans, cotton, corn, and rapeseed.
[0003] In the prior art, the synthesis process of glyphosate mainly includes the glycine method and the IDA (iminodiacetic acid) method. Compared with the IDA method, the glycine method uses less raw materials for preparing glyphosate, has a simpler synthesis process, and has a relatively low production cost. The raw material for producing glyphosate by the IDA method is mainly diethanolamine, and most of the diethanolamine is imported, which increases the uncertainty of production costs. In addition, the production conditions of the IDA method are relatively harsh, and have high requirements for production equipment and operating conditions. However, the glycine method will produce a large amount of wastewater in the process. These wastewaters contain high concentrations of pollutants, such as salts, organic matter, etc., which are difficult to handle and easily pollute the environment. At the same time, compared with the IDA method, the glycine method has a relatively low production efficiency. Summary of the invention
[0004] In order to solve the problems mentioned in the above background technology, the present invention provides a production system of glyphosate technical.
[0005] In order to achieve the above object, the present invention adopts the following technical solutions:
[0006] A production system of glyphosate technical comprises the following steps:
[0007] S1, phosphorus trichloride process: chlorine gas and liquid yellow phosphorus are introduced into a chlorination kettle, yellow phosphorus and chlorine gas undergo an exothermic reaction to generate phosphorus trichloride, the reaction temperature is controlled to obtain gaseous phosphorus trichloride, the gaseous phosphorus trichloride is introduced into a phosphorus washing tower for dephosphorization, liquid phosphorus and gaseous phosphorus trichloride after dephosphorization are obtained, a small amount of free phosphorus contained therein is converted into liquid phosphorus, the liquid phosphorus is collected at the bottom of the phosphorus washing tower, and is pressed back into the chlorination kettle through a reflux pipe for reuse, the gaseous phosphorus trichloride after dephosphorization is introduced into a condenser for condensation, a part of which is refluxed to the chlorination kettle, and a part of which enters a finished product tank to obtain liquid phosphorus trichloride;
[0008] S2, dimethyl phosphite process: under high vacuum, methanol and liquid phosphorus trichloride are introduced into an esterification kettle for esterification reaction to obtain esterification reaction materials and esterification tail gas, the esterification reaction materials enter the deacidification process for deacidification to obtain crude product and deacidification tail gas, the crude product is distilled and condensed to obtain dimethyl phosphite, the esterification tail gas and deacidification tail gas enter the tail gas recovery process, first spray water to recover hydrochloric acid, the obtained hydrochloric acid is stored in a storage tank, and then 10% sodium hydroxide alkali solution is used for alkali washing to obtain sodium chloride solution, and finally dried with 98% sulfuric acid to obtain 81% sulfuric acid, and the dried tail gas is compressed and liquefied and then recovered to the methyl chloride storage tank;
[0009] S3. Glyphosate process: Add paraformaldehyde into a synthesis kettle, then add methanol and triethylamine, raise the temperature, add glycine, dimethyl phosphite and a composite catalyst in sequence, stir to react, and obtain a synthesis liquid. Pass the synthesis liquid into a hydrolysis kettle, dealcoholize it with 31% hydrochloric acid, and then pass it into a crystallization kettle to cool it down. After standing, filter it, and dry it to obtain solid glyphosate. At the same time, the mother liquor obtained by hydrolysis and crystallization is recovered.
[0010] Furthermore, the reaction temperature in step S1 is 80-82° C., and the reaction time is 1-3 h. The reaction temperature in step S3 is 40-50° C., and the reaction time is 3-4 h.
[0011] Furthermore, the flow rate of chlorine gas introduced in step S1 is 100-200 mL / min.
[0012] Furthermore, in step S2, the vacuum degree is less than 1 mmHg, and the esterification reaction time is 2-4 hours.
[0013] Furthermore, in step S2, the feed mass ratio of methanol to liquid phosphorus trichloride is 1:(4-5).
[0014] Furthermore, in step S3, the feed mass ratio of paraformaldehyde, methanol, triethylamine, glycine, dimethyl phosphite and composite catalyst is (28-30): (32-35): (101-103): (70-75): (120-122): (10-20).
[0015] Furthermore, the composite catalyst in step S3 is prepared by the following steps:
[0016] A1. Add purified terephthalic acid and 1,4-butanediol to an esterification kettle, add tetrabutyl titanate, control the reaction temperature to 200-240° C., and the pressure to 0.2-0.5 MPa. During the reaction, continuously remove the generated water. After the reaction is completed, transfer the esterification product to a polycondensation reactor, carry out a polycondensation reaction at 250-280° C. and a vacuum degree of <1 mmHg, and continuously remove water to obtain polybutylene terephthalate;
[0017] A2, adding itaconic acid and polybutylene terephthalate into a reaction kettle filled with dimethylformamide solvent, adding a titanate catalyst, controlling the reaction temperature to 135-145°C, keeping warm and stirring for 3 hours, cooling to room temperature after the reaction, pouring the product into anhydrous ethanol for precipitation, and washing with anhydrous ethanol several times to obtain a copolymer;
[0018] A3. Add the copolymer to dimethylformamide, heat to 90-95°C and stir until the copolymer is completely swollen, add tributyl boron and ethylene glycol diglycidyl ether, continue stirring the reaction at a stirring speed of 200 rpm for 1-2 hours, cool to room temperature, pour the product into anhydrous ethanol for precipitation, wash with anhydrous ethanol several times, and dry in a vacuum drying oven at 60°C to constant weight to obtain a composite catalyst.
[0019] Furthermore, in step A1, the feed mass ratio of purified terephthalic acid, 1,4-butanediol and tetrabutyl titanate is (16-17): (10-11): (0.08-0.12).
[0020] Furthermore, in step A2, the mass ratio of itaconic acid, polybutylene terephthalate, dimethylformamide and titanate catalyst is (1-1.1):(12.6-13):25:(0.1-0.2).
[0021] Furthermore, the titanate catalyst in step A2 includes one or more of titanate coupling agent HY109, titanate coupling agent 105, titanate coupling agent 311 and titanate coupling agent NDZ-201.
[0022] Furthermore, in step A3, the mass ratio of the copolymer, dimethylformamide, tributyl boron and ethylene glycol diglycidyl ether is (10-12):20:(2-4):(0.05-0.08).
[0023] Beneficial effects of the present invention:
[0024] 1. In the technical solution of the present invention, polybutylene terephthalate (PBT) is synthesized from purified terephthalic acid and 1,4-butanediol through esterification and polycondensation to form a high molecular weight linear polymer. The introduction of itaconic acid (ITA) breaks the singleness of the PBT molecular chain and forms a PBT-ITA copolymer. The molecular chain of the copolymer contains both PBT segments and ITA segments, which increases the complexity and diversity of the molecular chain and enhances the adsorption and activation ability of the catalyst. The PBT-ITA copolymer provides a large number of active sites, which can adsorb and activate the reactant molecules, reduce the activation energy of the reaction, and thus accelerate the reaction rate. Through the cross-linking reaction of tributyl boron and ethylene glycol diglycidyl ether, a stable cross-linked structure is formed between the copolymer molecular chains. The active sites in the cross-linked structure are more evenly distributed, which is conducive to the diffusion and adsorption of the reactant molecules on the catalyst surface and improves the catalytic efficiency.
[0025] 2. In the technical solution of the present invention, the cross-linked structure makes the active sites more evenly distributed, which is conducive to the full contact and reaction of the reactant molecules on the catalyst surface, and improves the catalytic efficiency. The cross-linked structure improves the mechanical strength and stability of the catalyst, making it less likely to break or deform during use, which helps the recovery and reuse of the catalyst and reduces production costs. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0027] Figure 1 It is a flow chart of the phosphorus trichloride process in the present invention;
[0028] Figure 2 It is a flowchart of the dimethyl phosphite process of the present invention;
[0029] Figure 3 It is a flow chart of the glyphosate process in the present invention. DETAILED DESCRIPTION
[0030] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0031] Unless otherwise specified, the raw materials used in the present invention are all conventional products purchased from the market.
[0032] Preparation Example 1
[0033] The composite catalyst comprises the following steps to prepare:
[0034] A1. Add 16 kg of purified terephthalic acid and 10 kg of 1,4-butanediol into an esterification kettle, add 0.08 kg of tetrabutyl titanate, control the reaction temperature to 200 ° C, and the pressure to 0.2 MPa. During the reaction, the generated water is continuously removed. After the reaction is completed, the esterification product is transferred to a polycondensation reactor, and a polycondensation reaction is carried out at 250 ° C and a vacuum degree of 0.5 mmHg, and water is continuously removed to obtain polybutylene terephthalate;
[0035] A2, 1kg of itaconic acid and 12.6kg of polybutylene terephthalate were added to a reactor containing 25kg of dimethylformamide solvent, 0.1kg of titanate coupling agent 105 was added, the reaction temperature was controlled to 135°C, the reaction was kept warm and stirred for 3h, after the reaction was completed, the reaction was cooled to room temperature, the product was poured into anhydrous ethanol for precipitation, and washed with anhydrous ethanol several times to obtain a copolymer;
[0036] A3. Add 10 kg of the copolymer to 20 kg of dimethylformamide, heat to 90 ° C and stir until the copolymer is completely swollen, add 2 kg of tributyl boron and 0.05 kg of ethylene glycol diglycidyl ether, continue stirring and reacting at a stirring speed of 200 rpm for 1 hour, cool to room temperature, pour the product into anhydrous ethanol for precipitation, wash with anhydrous ethanol several times, and dry in a vacuum drying oven at 60 ° C to constant weight to obtain a composite catalyst.
[0037] Preparation Example 2
[0038] The composite catalyst comprises the following steps to prepare:
[0039] A1. Add 16.5 kg of purified terephthalic acid and 10.5 kg of 1,4-butanediol to an esterification kettle, add 0.1 kg of tetrabutyl titanate, control the reaction temperature to 220 ° C, and the pressure to 0.3 MPa. During the reaction, the generated water is continuously removed. After the reaction is completed, the esterification product is transferred to a polycondensation reactor, and a polycondensation reaction is carried out at 260 ° C and a vacuum degree of 0.5 mmHg, and water is continuously removed to obtain polybutylene terephthalate;
[0040] A2, 1.05kg itaconic acid and 12.8kg polybutylene terephthalate were added to a reactor containing 25kg dimethylformamide solvent, 0.15kg titanate coupling agent HY109 was added, the reaction temperature was controlled to 140°C, the reaction was kept warm and stirred for 3h, after the reaction was completed, the reaction was cooled to room temperature, the product was poured into anhydrous ethanol for precipitation, and washed with anhydrous ethanol several times to obtain a copolymer;
[0041] A3. Add 11 kg of the copolymer to 20 kg of dimethylformamide, heat to 93 ° C and stir until the copolymer is completely swollen, add 3 kg of tributyl boron and 0.07 kg of ethylene glycol diglycidyl ether, continue stirring and reacting at a stirring speed of 200 rpm for 1.5 hours, cool to room temperature, pour the product into anhydrous ethanol for precipitation, wash with anhydrous ethanol several times, and dry in a vacuum drying oven at 60 ° C to constant weight to obtain a composite catalyst.
[0042] Preparation Example 3
[0043] The composite catalyst comprises the following steps to prepare:
[0044] A1. Add 17 kg of purified terephthalic acid and 11 kg of 1,4-butanediol into an esterification kettle, add 0.12 kg of tetrabutyl titanate, control the reaction temperature to 240 ° C, and the pressure to 0.5 MPa. During the reaction, the generated water is continuously removed. After the reaction is completed, the esterification product is transferred to a polycondensation reactor, and a polycondensation reaction is carried out at 280 ° C and a vacuum degree of 0.5 mmHg, and water is continuously removed to obtain polybutylene terephthalate;
[0045] A2, 1.1kg itaconic acid and 13kg polybutylene terephthalate were added to a reactor containing 25kg dimethylformamide solvent, 0.2kg titanate coupling agent 311 was added, the reaction temperature was controlled to 145°C, the reaction was kept warm and stirred for 3h, after the reaction was completed, the reaction was cooled to room temperature, the product was poured into anhydrous ethanol for precipitation, and washed with anhydrous ethanol several times to obtain a copolymer;
[0046] A3. Add 12 kg of the copolymer to 20 kg of dimethylformamide, heat to 95 ° C and stir until the copolymer is completely swollen, add 4 kg of tributyl boron and 0.08 kg of ethylene glycol diglycidyl ether, continue stirring and reacting at a stirring speed of 200 rpm for 2 hours, cool to room temperature, pour the product into anhydrous ethanol for precipitation, wash with anhydrous ethanol several times, and dry in a vacuum drying oven at 60 ° C to constant weight to obtain a composite catalyst.
[0047] Example 1
[0048] A production system of glyphosate technical, comprising the following steps:
[0049] S1, phosphorus trichloride process: chlorine gas is passed into a chlorination kettle filled with 50kg yellow phosphorus at a flow rate of 100mL / min, the reaction temperature is controlled to be 80°C, the reaction is carried out for 1h to obtain gaseous phosphorus trichloride, the gaseous phosphorus trichloride is passed into a phosphorus washing tower for dephosphorization, liquid phosphorus and gaseous phosphorus trichloride after dephosphorization are obtained, a small amount of free phosphorus contained therein is converted into liquid phosphorus, the liquid phosphorus is collected at the bottom of the phosphorus washing tower, and is pressed back into the chlorination kettle through a reflux pipe for reuse, the gaseous phosphorus trichloride after dephosphorization is passed into a condenser for condensation, a part of which is refluxed to the chlorination kettle, and a part of which enters a finished product tank to obtain liquid phosphorus trichloride;
[0050] S2, dimethyl phosphite process: under a high vacuum of 0.5 mmHg, 10 kg of methanol and 40 kg of liquid phosphorus trichloride are introduced into an esterification kettle for esterification reaction for 2 hours to obtain esterification reaction materials and esterification tail gas, the esterification reaction materials enter the deacidification process for deacidification to obtain a crude product and deacidification tail gas, the crude product is distilled and condensed to obtain dimethyl phosphite, the esterification tail gas and deacidification tail gas enter the tail gas recovery process, first spray water to recover hydrochloric acid, obtain hydrochloric acid and store it in a storage tank, then use 10% sodium hydroxide alkali solution for alkali washing to obtain sodium chloride solution, and finally use 98% sulfuric acid to dry to obtain 81% sulfuric acid, the dried tail gas is compressed and liquefied and then recovered to the methyl chloride storage tank;
[0051] S3, glyphosate process: add 28kg of paraformaldehyde into a synthesis kettle, add 32kg of methanol and 101kg of triethylamine, raise the temperature to 40°C, add 70kg of glycine, 120kg of dimethyl phosphite and 10kg of the composite catalyst prepared in Preparation Example 1 in sequence, stir and react at a speed of 50rpm for 3h to obtain a synthetic liquid, pass the synthetic liquid into a hydrolysis kettle, dealcoholize it with 31% hydrochloric acid, then pass it into a crystallization kettle to cool it down, let it stand, filter it, and dry it to obtain solid glyphosate, and at the same time, recycle the mother liquor obtained by hydrolysis and crystallization.
[0052] Example 2
[0053] A production system of glyphosate technical, comprising the following steps:
[0054] S1, phosphorus trichloride process: chlorine gas is passed into a chlorination kettle filled with 50kg yellow phosphorus at a flow rate of 150mL / min, the reaction temperature is controlled to be 81°C, and the reaction is carried out for 2h to obtain gaseous phosphorus trichloride, and the gaseous phosphorus trichloride is passed into a phosphorus washing tower for dephosphorization to obtain liquid phosphorus and gaseous phosphorus trichloride after dephosphorization, wherein a small amount of free phosphorus contained therein is converted into liquid phosphorus, and the liquid phosphorus is collected at the bottom of the phosphorus washing tower and is pressed back into the chlorination kettle through a reflux pipe for reuse, and the gaseous phosphorus trichloride after dephosphorization is passed into a condenser for condensation, a part of which is refluxed to the chlorination kettle, and a part of which enters a finished product tank to obtain liquid phosphorus trichloride;
[0055] S2, dimethyl phosphite process: under a high vacuum of 0.5 mmHg, 10 kg of methanol and 45 kg of liquid phosphorus trichloride are introduced into an esterification kettle for esterification reaction for 3 hours to obtain esterification reaction materials and esterification tail gas, the esterification reaction materials enter the deacidification process for deacidification to obtain a crude product and deacidification tail gas, the crude product is distilled and condensed to obtain dimethyl phosphite, the esterification tail gas and deacidification tail gas enter the tail gas recovery process, first spray water to recover hydrochloric acid, obtain hydrochloric acid and store it in a storage tank, then use 10% sodium hydroxide alkali solution for alkali washing to obtain sodium chloride solution, and finally use 98% sulfuric acid to dry to obtain 81% sulfuric acid, the dried tail gas is compressed and liquefied and then recovered to the methyl chloride storage tank;
[0056] S3, glyphosate process: add 29kg of paraformaldehyde into a synthesis kettle, add 33kg of methanol and 102kg of triethylamine, raise the temperature to 45°C, add 72.5kg of glycine, 121kg of dimethyl phosphite and 15kg of the composite catalyst prepared in Preparation Example 2 in sequence, stir and react at a speed of 50rpm for 3.5h to obtain a synthetic liquid, pass the synthetic liquid into a hydrolysis kettle, dealcoholize it with 31% hydrochloric acid, then pass it into a crystallization kettle to cool it, let it stand, filter it, and dry it to obtain solid glyphosate. At the same time, the mother liquor obtained by hydrolysis and crystallization is recovered.
[0057] Example 3
[0058] A production system of glyphosate technical, comprising the following steps:
[0059] S1, phosphorus trichloride process: chlorine gas is passed into a chlorination kettle filled with 50kg of yellow phosphorus at a flow rate of 200mL / min, the reaction temperature is controlled to be 82°C, and the reaction is carried out for 3h to obtain gaseous phosphorus trichloride, and the gaseous phosphorus trichloride is passed into a phosphorus washing tower for dephosphorization to obtain liquid phosphorus and gaseous phosphorus trichloride after dephosphorization, wherein a small amount of free phosphorus contained therein is converted into liquid phosphorus, and the liquid phosphorus is collected at the bottom of the phosphorus washing tower and is pressed back into the chlorination kettle through a reflux pipe for reuse, and the gaseous phosphorus trichloride after dephosphorization is passed into a condenser for condensation, a part of which is refluxed to the chlorination kettle, and a part of which enters a finished product tank to obtain liquid phosphorus trichloride;
[0060] S2, dimethyl phosphite process: under a high vacuum of 0.1 mmHg, 10 kg of methanol and 50 kg of liquid phosphorus trichloride are introduced into an esterification kettle for esterification reaction for 4 hours to obtain esterification reaction materials and esterification tail gas, the esterification reaction materials enter the deacidification process for deacidification to obtain a crude product and deacidification tail gas, the crude product is distilled and condensed to obtain dimethyl phosphite, the esterification tail gas and deacidification tail gas enter the tail gas recovery process, first spray water to recover hydrochloric acid, obtain hydrochloric acid and store it in a storage tank, then use 10% sodium hydroxide alkali solution for alkali washing to obtain sodium chloride solution, and finally use 98% sulfuric acid to dry to obtain 81% sulfuric acid, the dried tail gas is compressed and liquefied and then recovered to the methyl chloride storage tank;
[0061] S3, glyphosate process: add 30kg of paraformaldehyde into a synthesis kettle, add 32-35kg of methanol and 103kg of triethylamine, raise the temperature to 50°C, add 75kg of glycine, 122kg of dimethyl phosphite and 20kg of the composite catalyst prepared in Preparation Example 3 in sequence, stir and react at a speed of 50rpm for 4h to obtain a synthetic liquid, pass the synthetic liquid into a hydrolysis kettle, dealcoholize it with 31% hydrochloric acid, then pass it into a crystallization kettle to cool it down, let it stand, filter it, and dry it to obtain solid glyphosate. At the same time, the mother liquor obtained by hydrolysis and crystallization is recovered.
[0062] Comparative Example 1
[0063] The difference between this comparative example and Example 1 is that polybutylene terephthalate is used instead of the composite catalyst, and the remaining steps are the same as those in Example 1.
[0064] Comparative Example 2
[0065] The difference between this comparative example and Example 2 is that itaconic acid is used instead of the composite catalyst, and the remaining steps are the same as those in Example 2.
[0066] Comparative Example 2
[0067] The difference between this comparative example and Example 3 is that tributyl boron is used instead of the composite catalyst, and the remaining steps are the same as those in Example 3.
[0068] Referring to the experimental method of GB / T 12686-2017 "Glyphosate Technical Material", the project indicators of the glyphosate technical materials prepared in Examples 1-3 and Comparative Examples 1-3 were measured, and the results are shown in Table 1:
[0069] Table 1. Project index results of Examples 1-3 and Comparative Examples 1-3
[0070]
[0071] The yields of Examples 1-3 and Comparative Examples 1-3 were calculated, and the results are shown in Table 2:
[0072] Table 2. Yield results of Examples 1-3 and Comparative Examples 1-3
[0073] serial number Yield (%) Example 1 98.1 Example 2 98.2 Example 3 98.2 Comparative Example 1 96.4 Comparative Example 2 94.1 Comparative Example 3 93.9
[0074] As can be seen from Table 1, the mass fractions of glyphosate in Examples 1-3 are all between 98.32% and 98.42%, with high purity, while the mass fractions of glyphosate in Comparative Examples 1-3 are significantly lower. The mass fractions of formaldehyde in all Examples and Comparative Examples are low, and the differences are not large, indicating that the residual amount of formaldehyde is within a controllable range. The mass fractions of nitrosoglyphosate in Examples 1-3 are very low, indicating that less by-products are generated during the reaction. The mass fractions of nitrosoglyphosate in Comparative Examples 1-3 are significantly higher, indicating that more by-products are generated. The content of sodium hydroxide insolubles in all Examples and Comparative Examples is very low, indicating that the content of sodium hydroxide insoluble impurities in the product is less.
[0075] As can be seen from Table 2, the yields of Examples 1-3 are all between 98.1% and 98.2%, indicating that the conversion rate of the raw materials during the reaction is high, while the yields of Comparative Examples 1-3 are relatively low.
[0076] In Examples 1-3, the composite catalyst is composed of components such as polybutylene terephthalate, itaconic acid and tributyl boron, and there may be synergistic effects between the components, which improves the catalytic efficiency and selectivity. The active sites and coordination effects in the composite catalyst may be able to selectively catalyze specific reaction pathways, reduce the generation of by-products, and improve the purity and yield of the product.
[0077] In summary, the purity and yield of glyphosate were significantly improved by controlling the feed ratio of each raw material and the reaction conditions and using the composite catalyst prepared in the preparation example.
[0078] In the description of the specification, the description with reference to the terms "embodiment", "various embodiments" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or preparation example are included in at least one embodiment or preparation example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or preparation example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or preparation examples in a suitable manner.
[0079] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
Claims
1. A production system of glyphosate technical, characterized in that: The process includes a phosphorus trichloride process, a dimethyl phosphite process and a glyphosate process, and specifically includes the following steps: S1, phosphorus trichloride process: chlorine gas is passed into a chlorination kettle filled with yellow phosphorus, the reaction temperature is controlled to obtain gaseous phosphorus trichloride, the gaseous phosphorus trichloride is passed into a phosphorus washing tower for dephosphorization, liquid phosphorus and gaseous phosphorus trichloride after dephosphorization are obtained, the liquid phosphorus is collected at the bottom of the phosphorus washing tower, and is pressed back into the chlorination kettle through a reflux pipe for reuse, and the gaseous phosphorus trichloride after dephosphorization is passed into a condenser for condensation to obtain liquid phosphorus trichloride; S2, dimethyl phosphite process: under high vacuum, methanol and liquid phosphorus trichloride are introduced into an esterification kettle for esterification reaction to obtain esterification reaction materials and esterification tail gas, the esterification reaction materials enter the deacidification process for deacidification, and obtain crude products and deacidification tail gas, the crude products are distilled and condensed to obtain dimethyl phosphite, the esterification tail gas and deacidification tail gas enter the tail gas recovery process, and are recovered to the methyl chloride storage tank after hydrochloric acid recovery, alkali washing, drying, compression and liquefaction; S3, glyphosate process: add paraformaldehyde into a synthesis kettle, then add methanol and triethylamine, raise the temperature, add glycine, dimethyl phosphite and composite catalyst in sequence, stir to react, obtain synthesis liquid, pass the synthesis liquid into a hydrolysis kettle for dealcoholization, then pass into a crystallization kettle for cooling, let stand and then filter, dry to obtain solid glyphosate, and at the same time, recycle the mother liquor obtained by hydrolysis and crystallization.
2. A production system of glyphosate technical according to claim 1, characterized in that: The reaction temperature in step S1 is 80-82° C., and the reaction time is 1-3 h. The reaction temperature in step S3 is 40-50° C., and the reaction time is 3-4 h.
3. A production system of glyphosate technical according to claim 1, characterized in that: The flow rate of chlorine gas introduced in step S1 is 100-200 mL / min.
4. The production system of glyphosate technical according to claim 1, characterized in that: The vacuum degree in step S2 is less than 1 mmHg, and the esterification reaction time is 2-4 hours; the feeding mass ratio of methanol and liquid phosphorus trichloride in step S2 is 1:(4-5).
5. The production system of glyphosate technical according to claim 1, characterized in that: In step S3, the feed mass ratio of paraformaldehyde, methanol, triethylamine, glycine, dimethyl phosphite and composite catalyst is (28-30):(32-35):(101-103):(70-75):(120-122):(10-20).
6. The production system of glyphosate technical according to claim 1, characterized in that: The composite catalyst in step S3 comprises the following steps to prepare: A1. Add purified terephthalic acid and 1,4-butanediol to an esterification kettle, add tetrabutyl titanate, control the reaction temperature to 200-240° C., and the pressure to 0.2-0.5 MPa. During the reaction, continuously remove the generated water. After the reaction is completed, transfer the esterification product to a polycondensation reactor, carry out a polycondensation reaction at 250-280° C. and a vacuum degree of <1 mmHg, and continuously remove water to obtain polybutylene terephthalate; A2, adding itaconic acid and polybutylene terephthalate into a reaction kettle filled with dimethylformamide solvent, adding a titanate catalyst, controlling the reaction temperature to 135-145°C, keeping warm and stirring for 3 hours, cooling to room temperature after the reaction, pouring the product into anhydrous ethanol for precipitation, and washing with anhydrous ethanol several times to obtain a copolymer; A3. Add the copolymer to dimethylformamide, heat to 90-95°C and stir until the copolymer is completely swollen, add tributyl boron and ethylene glycol diglycidyl ether, continue stirring the reaction at a stirring speed of 200 rpm for 1-2 hours, cool to room temperature, pour the product into anhydrous ethanol for precipitation, wash with anhydrous ethanol several times, and dry in a vacuum drying oven at 60°C to constant weight to obtain a composite catalyst.
7. A production system of glyphosate technical according to claim 6, characterized in that: In step A1, the mass ratio of purified terephthalic acid, 1,4-butanediol and tetrabutyl titanate is (16-17): (10-11): (0.08-0.12).
8. The production system of glyphosate technical according to claim 6, characterized in that: In step A2, the mass ratio of itaconic acid, polybutylene terephthalate, dimethylformamide and titanate catalyst is (1-1.1):(12.6-13):25:(0.1-0.2).
9. The production system of glyphosate technical according to claim 6, characterized in that: The titanate catalyst in step A2 includes one or more of titanate coupling agent HY109, titanate coupling agent 105, titanate coupling agent 311 and titanate coupling agent NDZ-201.
10. A production system of glyphosate technical according to claim 6, characterized in that: In step A3, the mass ratio of the copolymer, dimethylformamide, tributyl boron and ethylene glycol diglycidyl ether is (10-12):20:(2-4):(0.05-0.08).